JP2001500567A - Molding materials, especially materials for the powder metallurgical production of highly wear-resistant valve seat rings or valve guides - Google Patents

Molding materials, especially materials for the powder metallurgical production of highly wear-resistant valve seat rings or valve guides

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JP2001500567A
JP2001500567A JP09516110A JP51611097A JP2001500567A JP 2001500567 A JP2001500567 A JP 2001500567A JP 09516110 A JP09516110 A JP 09516110A JP 51611097 A JP51611097 A JP 51611097A JP 2001500567 A JP2001500567 A JP 2001500567A
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weight
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molybdenum
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JP4272706B2 (en
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ケーラー エッケハルト
ダラル キリット
ヴイ ナドカルニ エニール
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SCM Metal Products Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Abstract

(57)【要約】 殊に高い耐摩耗性および耐蝕性ならびに高い熱伝導率を有する弁座環または弁案内部材を少なくとも５０重量％の銅含量を有する粉末混合物から粉末冶金的に製造するための材料；出発粉末混合物は、５０〜９０重量％の量の、Ｃｕ含量を有する基礎粉末および１０〜５０重量％の量の、モリブデンを含有する粉末状合金添加剤からなり、この場合基礎粉末は、０．１〜１．１重量％のＡｌ2Ｏ3含量を有する、Ａｌ2Ｏ3により分散固化された銅粉末であり、これは、Ｃｕ−Ａｌ溶融液を噴霧しかつ引続き酸化雰囲気中で加熱することに製造されたものである。更に、本発明の対象は、殊に高い熱伝導率を有する耐摩耗性および耐蝕性の弁座環または弁案内部材を粉末冶金的に製造するための前記種類の分散固化された粉末の使用ならびにこの種の弁座環または弁案内部材の製造法である。 (57) Abstract: A powder metallurgical process for producing valve seat rings or valve guides having particularly high wear and corrosion resistance and high thermal conductivity from powder mixtures having a copper content of at least 50% by weight. Materials; the starting powder mixture consists of a base powder with a Cu content in an amount of 50-90% by weight and a powdered alloy additive containing molybdenum in an amount of 10-50% by weight, wherein the base powder comprises: Al 2 O 3 dispersed and solidified copper powder having an Al 2 O 3 content of 0.1 to 1.1% by weight, which is sprayed with a Cu—Al melt and subsequently heated in an oxidizing atmosphere It is manufactured to be. Furthermore, the object of the present invention is the use of dispersed solidified powders of the above type for the powder metallurgical production of wear- and corrosion-resistant valve seat rings or valve guides, in particular with high thermal conductivity, and This is a method of manufacturing such a valve seat ring or valve guide member.

Description

【発明の詳細な説明】 成形材料、殊に高い耐摩耗性を有する弁座環または弁案内部材を粉末冶金的に製 造するための材料 本発明は、高い熱伝導性ならびに高い耐摩耗性および耐腐食性を有する成形材 料を、少なくとも約５０重量％の銅含量を有する粉末混合物の圧縮、焼結および 場合によっては後圧縮によって粉末冶金的に製造するための材料に関する。 この種の焼結材料は、熱いガスまたはガス混合物に晒されている成形部材のた め、例えば一方で高い機械的負荷、他方で同時に熱い燃焼ガスの作用に晒されて いる内燃機関用の弁座環および弁座案内部材の製造のために必要とされている。 従って、この種の焼結材料は、耐摩耗性および耐蝕性であるだけでなく、高い熱 伝導性をも有する材料から製造されていなければならない。この場合、熱伝導性 は、ますます重要な意味を持っている。それというのも、弁に対する温度水準は 、排出の理由から化学量論的混合物の必要とされる拡充によって上昇され、かつ よりいっそう高い出力のエンジンに対して持続傾向が認められうるからである。 弁座環が挿入されている、弁の頭部とシリンダー頭部との間の温度差を弁内で の熱伝達によって減少させることは、公知である。この目的のために、弁軸には 、中空孔が備えられており、弁軸は冷却される。費用よび重量の理由から、弁軸 の直径は、最近、多くの場合には、弁軸に中空孔を備えることがもはや不可能で あるような程度に縮小されており、したがって中空穿孔されかつ例えばナトリウ ムが充填された弁は、将来的にはもはや不可能なものとなる。従って、こうして 熱を迅速に導出し、温度水準を減少させ、摩擦比を改善し、かつ系を技術的かつ 費用的に改善するために、弁座、殊に弁座環を製造する材料の熱伝導性を改善す ることが努力されている。 注入された銅を有する鉄を基礎とする焼結材料からなる粉末冶金的に製造され た成形部材は、公知であり、この成形部材は、弁座環または弁案内部材として使 用するために十分な耐摩耗性を有するが、その熱伝導性は、銅含量を有しない焼 結材料と比較して十分な高さを持っていない。例えば、ドイツ連邦共和国特許第 ２１１４１６０号明細書の記載から、炭素および鉛ならびに別の合金成分が添加 されている、鉄を基礎とする材料からなる焼結材料は、公知である。この材料か ら製造された弁座環は、実際に十分な耐熱性および耐摩耗性を有しているが、し かし、その熱伝導性は、本明細書中で殊に現在の内燃機関の排出範囲内で懸案と なっている問題を解決するためには十分なものではない。 PCT-EP89/01343の記載から、耐摩耗性が高い際に高 められた熱伝導性を有する弁座環を粉末冶金的に製造するための焼結材料は、公 知である。焼結材料は、銅約７０〜１００重量％の銅含量および１つの合金含量 を有する基礎金属粉末からなる。この合金含量は、例えばコバルト１〜３重量％ または硬質相としての基礎金属粉末が混合されている高合金の添加金属粉末から なり、この場合この含量は、最大３０重量％である。 この種の材料を用いて実施される試験により、この材料は、弁座環の完成、殊 に内燃機関の排出範囲にとっては不十分な耐摩耗性を有することが判明した。こ のことは、実際に、１５０μｍの最大粒径を有する硬質材料の埋封によるマトリ ックスの強化によって材料の硬度を上昇させることができ、ひいては弁座環の耐 摩耗性も上昇させることできるが、しかし、別の側での対向体の比較的に大きく 角のとがった埋封物によって著しく摩耗されることに帰因する。従って、弁座環 の耐摩耗性は僅かであり、他方で、系の永続的な機能にとって重要な全体的な耐 摩耗性を劣化させた。 本発明の課題は、殊に耐摩耗性が著しく高くかつ同時にこの目的のために利用 される公知の焼結材料と比較して著しく高い熱伝導性を有する弁座環または弁案 内部材を粉末冶金的に製造するための焼結材料を得ることであった。 本発明は、少なくとも約５０重量％の銅含量を有する出発粉末混合物の圧縮、 焼結および場合によっては 後圧縮により、高い耐摩耗性および耐蝕性ならびに高い熱伝導率を有する成形部 材を粉末冶金的に製造するため、殊に内燃機関用の弁座環または弁案内部材を製 造するための材料から出発し、出発粉末混合物が５０〜９０重量％の量の、Ｃｕ 含量を有する基礎粉末および１０〜５０重量％の量の、モリブデンを含有する粉 末状合金添加剤からなり、かつ合金粉末が分散固化された銅粉末であることにあ る。有利に、分散固化された銅粉末は、Ａｌ2Ｏ3０．１〜１．１重量％および不 純物０．５重量％を含有するＡｌ2Ｏ3によって固化されており、Ｃｕ−Ａｌ溶融 液を噴霧しかつ引続きアルミニウムの選択的な酸化のために酸化雰囲気中で加熱 することに製造される。 本発明は、一定の方法で特にＡｌ2Ｏ3を用いて分散固化されたＣｕ−Ａｌ2Ｏ3 粉末を形成部材の粉末冶金的な製造のための材料として使用することにより、一 面で高い耐摩耗性および耐腐食性を有し、他面、高い熱伝導率を有する製品を生 じるという意外な認識に基づくものであり、したがってこの材料は、殊に内燃機 関用の弁座環または弁案内部材の製造に適している。 本発明の使用目的には、Ａｌ2Ｏ3が分散固化されたＣｕ粉末を有するもののみ が適当であり、この場合この粉末は、例えば米国特許第３７７９７１４号明細書 またはドイツ連邦共和国特許第２３５５１２２号明 細書の記載から公知の方法により、Ｃｕ−Ａｌ溶融液の噴霧により製造されたＣ ｕ−Ａｌ合金化された粉末を内部酸化しかつ引続き酸化雰囲気中で加熱すること によって製造されたものであり、他方、内部酸化が明らかに排除されている、英 国特許第２０８３５００号明細書に記載の別の方法により製造された分散固化さ れた金属粉末は、不適当なものである。本出願人としては、内部酸化により製造 されたＣｕ−Ａｌ2Ｏ3粉末の場合に銅マトリックス中に分散されたＡｌ2Ｏ3粒子 間の距離が３〜１２ｎｍの程度の大きさであり、他方、内部酸化なしに製造され た粉末の場合には、約４０μｍであるということに帰結した。成形部材、殊に弁 座環または弁案内部材を粉末冶金的に製造するための基礎粉末として分散固化さ れた金属を本発明により使用することについては、前記刊行物には、何等の指摘 もない。 本発明の１つの好ましい実施態様によれば、合金添加剤がモリブデン２８〜３ ２重量％、有利に３０重量％、クロム９〜１１重量％、有利に１０重量％、珪素 ２．５〜３．５重量％、残分コバルトからの粉末状の、有利に水噴霧された金属 間硬質相からなることが設けられており、この場合粉末混合物中の金属間硬質相 は、約１０重量％の量であり、かつ基礎粉末は、約９０重量％の量である。 本発明の別の実施態様の場合には、金属間硬質相は 、モリブデン２８〜３２重量％、有利に３０重量％、クロム９〜１１重量％、有 利に１０重量％、珪素２．５〜３．５重量％、有利に３重量％、残分鉄からなり 、この場合粉末混合物中の金属間相は、約１０重量％の量であり、かつ基礎粉末 は、約９０重量％の量である。 また、合金添加剤は、本発明によれば、タングステン約６重量％.、モリブデ ン約５重量％、バナジウム約２重量％、クロム約４重量％、残分鉄の高速度鋼粉 末からの硬質相からなることもでき、この場合粉末混合物中の硬質相は、約３０ 重量％までの量であり、かつ基礎粉末は、約７０重量％またはそれ以上の量であ る。 また、合金添加剤は、モリブデン約１１重量％、燐約０．６重量％、炭素約１ ．２重量％、残分鉄のＭｏ−Ｐ−Ｃ粉末からの硬質相からなることができ、この 場合粉末混合物中の硬質相および基礎粉末は、それぞれ約５０重量％の量である 。 更に、本発明の対象は、基礎粉末約８０重量％、モリブデン粉末約１０重量％ および銅粉末約１０重量％または基礎粉末約７９重量％、モリブデン粉末約１０ 重量％、銅粉末約１０重量％および粉末状三酸化モリブデン約１重量％の出発粉 末混合物からなる材料である。 更に、本発明には、基礎粉末が付加的に二硫化モリ ブデン（MoS2）および／または硫化マンガン（MnS）および／または二硫化タン グステン（WS2）および／またはフッ化カルシウム（CaF2）および／またはテル ル（Te）および／または炭酸カルシウム（CaCO3）を基礎粉末の量に対して少な くとも１重量％ないし最大３重量％の全体量で含有することが設けられている。 更に、本発明の対象は、高い耐摩耗性および耐蝕性ならびに高い熱伝導率を有 する成形部材を粉末冶金的に製造するため、殊に内燃機関用の弁座環または弁案 内部材を製造するための１つの方法であり、この場合出発粉末混合物は、圧縮を 簡易化する薬剤、例えばワックス０．３重量％を有する前記に記載の組成物と混 合され、変形され、かつ約８．０ｇ／ｃｍ3である密度を有する成形部材に圧縮 され、引続き保護ガス下で焼結され；この場合、焼結は、有利に窒素約８０重量 ％および水約２０重量％からなる保護ガス雰囲気下で約１０４０℃の温度で約４ ５分間行なわれる。場合によっては、焼結された成形部材は、約８．８ｇ／ｃｍ3 の密度に後圧縮される。 本発明の選択的な実施態様によれば、請求項１に記載された出発粉末が次に記 載された物質または物質混合物の１つまたはそれ以上を含有することが設けられ ている： ａ）工具鋼 型 Ｍ３５または型 Ｔ１５、 Ni-Cr-Si-Fe-B-Cu-Mo ５〜３０重量％； ｂ）W、Mo、Nb、WC、TiC、B4C、TIC、c-VN、TiB2 ５〜１０重量％； ｃ）Ti、Cr、Zr、Cr＋Zr、Be、Ni＋P ０．５〜５重量％。 群ａ）の材料は、前記添加剤を銅中に拡散混入することにより分散固化された 銅の銅マトリックスで合金化されたものであり、この場合導電率および熱伝導率 は、著しく減少されている。熱伝導率を１００Ｗ／ｍ・ｋを上廻るように維持す るために、前記添加剤の含量は、５〜２０重量％、典型的には１０重量％を超え てはならない。 群ｂ）の材料は、銅マトリックスで合金化されておらず、したがって熱伝導率 に対する顕著な影響を示さない。しかし、この材料は、比較的に安価である。勿 論、５〜１０重量％の含量で十分であることが判明した。 群ｃ）の添加剤は、金属間成分の分離を生じさせ、こうして付加的に分散固化 された銅中でのＡｌ2Ｏ3粒子による硬化のために硬度の効果を重ねて生じさせる 。酸化アルミニウム粒子は、高い温度（＞５００℃）で銅マトリックスの効果的 な硬化を生じさせるけれども、分離段階は、中位の温度範囲（２００〜５００℃ ）内で効果的な硬化を生じさせ、この場合には、弁座環が晒される典型的な運転 温度が問題となる。より 高い高温硬さにより、一般により高い耐摩耗性が生じる。 弁座環の耐摩耗性を、固体滑剤、例えばグラファイト、ＭｏＳ2、ＭｎＳ、ｈ −ＢＮ、ＣａＦ2等並びに金属添加物、例えばＭｏ、Ｃｏ、Ｗ等の添加によって も生じさせることができ、これらは運転温度で、潤滑効果を有する酸化物皮膜を 形成する。 出発粉末が１種以上の次に挙げる物質： Ｚｎ５〜２０重量％、元素のＡｌ、Ｂｅ、Ｓｉ、Ｍｇ、Ｓｎのいずれか０． １〜５重量％ を含有することにより、耐酸化性、即ち耐腐食性が運転中にかなり高められる。 熱伝導率の可能な限り僅かな低減に関して、Ｚｎは有利な合金成分である。これ に関して、５〜３０重量％の添加は問題ない。 出発粉末は、不均一な粒子形を有する次に記載の粉末状物質１種以上を含有す るのが有利である： 高生強度Ｃｕ、電解Ｃｕ、酸化物還元Ｃｕ、Ｍｏ等５〜２５重量％。 使用される分散固化銅が円形粒子、平滑粒子を有することで、これらの材料か らなる未焼結の生成形体は僅かな強度を有するにすぎない。生強度は、前記の成 分を添加することによりかなり高めることができる。「高生強度Ｃｕ」とは、繊 維様に長く薄い粒子を有する粉末であり、これは圧縮すると互いに絡み合い、か つそれにより、生成形体の高い強度が生じる。熱伝導 率は、純粋なＣｕの添加により影響を受けず、５〜２５重量％添加することがで き、その際、有利な範囲は１０〜１５重量％である。 分散固化銅の加工性、殊に切削性は、次に挙げる物質の１種以上を添加するこ とにより改善される： ａ）化学元素、例えばＣ（グラファイト）、Ｔｅ、Ｓｅ０．２〜２重量％； ｂ）スルフィド、例えばＭｏＳ2、ＭｎＳ等０．５〜５重量％； ｃ）酸化物、例えばＭｏＯ3、ＷＯ3、Ｃｏ3Ｏ4等０．５〜５重量％； ｄ）化合物、例えば六方晶ＢＮ、ＣａＦ2０．５〜５重量％。 殊に弁頭部での圧縮の場合に与えられているべき弁座環の放射状破壊強度は、 次の物質１種以上の添加により高められる： ａ）Ｚｎ５〜２０重量％、Ａｌ又はＳｎ０．１〜５重量％等； ｂ）Ｍ３５又はＴ１５タイプの工具鋼、Ｎｉ−Ｃｒ−Ｓｉ−Ｆｅ−Ｂ−Ｃｕ −Ｍｏ５〜３０重量％。 前記の合金添加物の相応する組合せにより、出発粉末混合物をそれぞれ弁座環 に求められる特性に関して、最適に調節することができる。 全て前記した本発明による粉末混合物では、弁座環 の製造に関する主な利点は、熱伝導率が特に高い、即ち最低１００Ｗ／ｍ・ｋで あることにある。 実施例 例１ Ａｌ2Ｏ3０．５重量％の含有率を有する、内部酸化により分散固化されたＣｕ −Ａｌ2Ｏ3−粉末を、慣用の圧縮簡易化剤０．３重量％と混合し、かつ８００Ｍ Ｎ／ｍｍ2の圧縮圧力で、寸法３６．６×３０．１×９ｍｍの弁座環に圧縮した 。８．４ｇ／ｃｍ3の圧縮密度を有する生成形体を引き続き４５分間、温度１０ ４０℃で、Ｎ2８０％及び水素２０％からなる保護ガス雰囲気下に焼結した。焼 結密度は、８．４ｇ／ｃｍ3であった。焼結された環を引き続き、圧力１６００ ＭＮ／ｍｍ2の圧力で後圧縮して、密度８．８ｇ／ｃｍ3にした。 第１表は測定された密度及び硬度を、第２表は、レーザー−フラッシュ法によ り測定された熱伝導率の値を示している。 例２ 内部酸化によりＡｌ2Ｏ3０．５重量％の含有率を有して製造された分散固化Ｃ ｕ−Ａｌ2Ｏ3−粉末９０重量％を、水蒸発された粉末状金属間硬質相１０重量％ 及び慣用の圧縮簡易化剤０．３重量％と混合した。金属間硬質相は、コバルト６ ０重量％、モリブデン３０重量％、クロム１０重量％及びケイ素３重量％からな った。粉末混合物を圧縮圧力８００ＭＮ／ｍｍ2で、寸法３６．６×３０．１× ９ｍｍの弁座環に圧縮した。生成形体は圧縮密度８．２ｇ／ｃｍ3を有した。引 き続き、環を４５分間、温度１０４０℃で、Ｎ2８０％及びＨ2２０％からなる保 護ガス雰囲気中で焼結させ；焼結密度は８．２ｇ／ｃｍ3であった。８．７ｇ ／ｃｍ3の密度への後圧縮は、圧力１６００ＭＮ／ｍｍ2の圧力で行った。 第３表は密度及び硬度の値を、第４表はレーザー−フラッシュー法で測定され た熱伝導率の値を示している。 例１及び２により製造された弁座環は、銅注入を場 合により伴う鉄をベースとする市販の弁座環に比べて熱伝導率の予期せぬ改善を 示した。これは、図面１から明らかである。曲線１は例１による弁座環の熱伝導 率の値を、曲線２は例２による環に関する値を、曲線３は銅注入を伴うＦｅをベ ースとする弁座環の値を、かつ曲線４は本出願人の市販の弁座環の値を示してい る。 例１により製造された環は、内燃機関の入口領域でのその使用が可能な硬度を 有し、一方で、例２による弁座環は、出口領域で使用することができ、かつこの 場合、優れた走行特性を有する。このことは実験により判明したが、その条件を 第５表にまとめた。 機関実験の結果を第６表にまとめ、かつ図２に図示 した。陥没深さは、弁及び弁座環の磨滅の合計である。例２による本発明の弁座 環を、大規模に使用されている本出願人の量産材料Como 12と比較した。 本発明の弁座環の陥没深さは、材料の熱伝導率がかなり上昇すると、市販の弁 座環の陥没深さより低くなることが判明した。DETAILED DESCRIPTION OF THE INVENTION Molding materials, especially valve rings or valve guides with high wear resistance, are produced by powder metallurgy. Materials for building   The present invention relates to a molded material having high thermal conductivity and high wear and corrosion resistance. The powder is pressed, sintered and mixed with a powder mixture having a copper content of at least about 50% by weight. In some cases, it relates to materials for powder metallurgical manufacture by post-compression.   This type of sintered material is used for forming parts that are exposed to hot gases or gas mixtures. For example, on the one hand, high mechanical loads and, on the other hand, simultaneously exposed to the action of hot combustion gases There is a need for the manufacture of valve seat rings and valve seat guides for certain internal combustion engines. Therefore, this type of sintered material is not only wear and corrosion resistant, but also has high heat It must be made from a material that is also conductive. In this case, the thermal conductivity Has an increasingly important meaning. Because the temperature level for the valve is Increased by the required expansion of the stoichiometric mixture for emission reasons, and This is because a sustained tendency can be observed for engines with higher power.   The temperature difference between the head of the valve and the head of the cylinder in which the valve seat ring is inserted It is known to reduce by heat transfer. For this purpose, the valve stem has , A hollow hole is provided, and the valve shaft is cooled. For cost and weight reasons, the valve stem In recent years, it is often no longer possible to provide hollow holes in the valve stem It has been reduced to some extent, and is therefore hollow perforated and, for example, sodium Filled valves will no longer be possible in the future. So in this way Quickly extract heat, reduce temperature levels, improve friction ratios, and make systems technical and In order to improve the cost, the thermal conductivity of the material from which the valve seat, in particular the valve seat ring is made, should be improved. Efforts are being made.   Manufactured by powder metallurgy consisting of iron-based sintered material with injected copper Molded members are known and are used as valve seat rings or valve guides. It has sufficient wear resistance to be used, but its thermal conductivity is It does not have enough height compared to the bonding material. For example, German Patent No. From the description of 2114160, carbon and lead and other alloy components are added Sintered materials made of iron-based materials are known. This material Although the valve seat rings manufactured from these products actually have sufficient heat and wear resistance, However, its thermal conductivity is a concern here, especially within the current range of emissions of internal combustion engines. Is not enough to solve the problem.   From the description of PCT-EP89 / 01343, it is Sintered materials for powder metallurgical production of valve rings with thermal conductivity Is knowledge. The sintered material has a copper content of about 70-100% by weight copper and one alloy content Consisting of a base metal powder having The alloy content is, for example, 1 to 3% by weight of cobalt. Or from a high alloy additive metal powder in which the base metal powder as a hard phase is mixed In this case, this content is at most 30% by weight.   Tests conducted with this type of material have shown that this material can be used to complete valve seat rings, especially It has been found that they have insufficient wear resistance for the emission range of the internal combustion engine. This This actually means that the matrices due to the embedding of hard material with a maximum particle size of 150 μm The hardness of the material can be increased by strengthening the housing, and the resistance of the valve seat ring Abrasion can also be increased, but the counterpart on the other side is relatively large Attributable to significant wear due to the pointed inserts. Therefore, the valve seat ring Has a low abrasion resistance, while the overall resistance is important for the permanent functioning of the system. Deterioration of wear properties.   The object of the present invention is to provide a particularly high wear resistance and at the same time use for this purpose. Seat ring or valve plan having significantly higher thermal conductivity compared to known sintered materials It was to obtain a sintered material for manufacturing the inner member by powder metallurgy.   The present invention provides for the compression of a starting powder mixture having a copper content of at least about 50% by weight; Sintering and possibly Molded parts with high abrasion and corrosion resistance and high thermal conductivity due to post-compression In order to produce the material in powder metallurgy, a valve seat ring or valve guide, in particular for an internal combustion engine, is produced. Starting from the material to be prepared, the starting powder mixture is in an amount of 50 to 90% by weight of Cu Base powder with content and powder containing molybdenum in an amount of 10 to 50% by weight The alloy powder is composed of a powdery alloy additive, and the alloy powder is a dispersed and solidified copper powder. You. Advantageously, the dispersed and solidified copper powder comprises AlTwoOThree0.1-1.1% by weight and Al containing 0.5% pure by weightTwoOThreeSolidified by Cu-Al melting Spray liquid and subsequently heat in oxidizing atmosphere for selective oxidation of aluminum To be manufactured.   The present invention provides a method,TwoOThreeCu-Al dispersed and solidified usingTwoOThree The use of powder as a material for the powder metallurgical production of formed parts Products with high abrasion and corrosion resistance on the other side and high thermal conductivity on the other side. This material is particularly useful for internal combustion engines. It is suitable for manufacturing valve seat rings or valve guide members for use.   The purpose of the present invention is to use AlTwoOThreeHaving only Cu powder dispersed and solidified In this case, the powder is, for example, described in US Pat. No. 3,779,714. Or DE 2355122 A1 C produced by spraying a Cu-Al melt by a method known from the detailed description internally oxidizing the u-Al alloyed powder and subsequently heating in an oxidizing atmosphere Manufactured on the other hand, while internal oxidation is clearly excluded. Dispersion solidification produced by another method described in US Patent No. 2083500 The resulting metal powder is unsuitable. Applicant, manufactured by internal oxidation Cu-AlTwoOThreeAl dispersed in a copper matrix in the case of powderTwoOThreeparticle The distance between them is of the order of 3 to 12 nm, while being manufactured without internal oxidation. In the case of the powder, the result was about 40 μm. Molded parts, especially valves Dispersed and solidified as the base powder for powder metallurgy manufacture of washer or valve guide There is no indication in the above publication about the use of Nor.   According to one preferred embodiment of the present invention, the alloying additive is molybdenum 28-3 2% by weight, preferably 30% by weight, chromium 9-11% by weight, preferably 10% by weight, silicon 2.5-3.5% by weight, powdered, preferably water-sprayed metal from the balance cobalt In which the intermetallic hard phase in the powder mixture is provided. Is about 10% by weight and the base powder is about 90% by weight.   In another embodiment of the present invention, the intermetallic hard phase is , Molybdenum 28-32% by weight, preferably 30% by weight, chromium 9-11% by weight, yes 10% by weight, 2.5-3.5% by weight of silicon, preferably 3% by weight, with the balance being iron The intermetallic phase in the powder mixture is in an amount of about 10% by weight and the base powder Is in an amount of about 90% by weight.   Also, according to the present invention, the alloy additive comprises about 6% by weight of tungsten, molybdenum. About 5% by weight, about 2% by weight of vanadium, about 4% by weight of chromium, high-speed steel powder of residual iron The hard phase in the powder mixture may comprise about 30 %, And the base powder is present in an amount of about 70% by weight or more. You.   The alloy additives were about 11% by weight molybdenum, about 0.6% by weight phosphorus, and about 1% carbon. . 2% by weight, consisting of a hard phase from Mo-PC powder with the balance iron, The hard phase and the base powder in the powder mixture are each in an amount of about 50% by weight .   Further, the subject of the present invention is about 80% by weight of base powder, about 10% by weight of molybdenum powder. And about 10% by weight of copper powder or about 79% by weight of base powder, about 10% by weight of molybdenum powder. Starting powder of about 10% by weight of copper powder and about 1% by weight of molybdenum trioxide in powder form It is a material consisting of a powder mixture.   Furthermore, the present invention provides that the base powder additionally comprises Buden (MoSTwo) And / or manganese sulfide (MnS) and / or tan disulfide Gusten (WSTwo) And / or calcium fluoride (CaFTwo) And / or tell (Te) and / or calcium carbonate (CaCOThree) Less than the amount of the base powder It is provided that the total content be at least 1% by weight up to 3% by weight.   Furthermore, the objects of the present invention have high abrasion and corrosion resistance and high thermal conductivity. Valve rings or valve designs for powder metallurgical production of molded parts to be produced, in particular for internal combustion engines One method for manufacturing the inner part, where the starting powder mixture is compressed Mixing with the composition described above having a simplification agent, for example 0.3% by weight of wax. Combined, deformed, and about 8.0 g / cmThreeCompressed into molded parts with a certain density And subsequently sintered under protective gas; in this case, the sintering is advantageously about 80% by weight of nitrogen % At a temperature of about 1040 ° C. in a protective gas atmosphere consisting of about 20% by weight of water and about 20% by weight of water. Performed for 5 minutes. In some cases, the sintered molded part has a weight of about 8.8 g / cm.Three After compression to a density of   According to an alternative embodiment of the present invention, the starting powder according to claim 1 is as follows: Containing one or more of the listed substances or substance mixtures ing: a) Tool steel type M35 or type T15,     Ni-Cr-Si-Fe-B-Cu-Mo     5-30% by weight; b) W, Mo, Nb, WC, TiC, BFourC, TIC, c-VN, TiBTwo     5-10% by weight; c) Ti, Cr, Zr, Cr + Zr, Be, Ni + P     0.5-5% by weight.   The materials of group a) were dispersed and solidified by diffusing the additives into copper. Alloyed with a copper matrix of copper, where the electrical and thermal conductivity Has been significantly reduced. Maintain thermal conductivity above 100 W / mk In order to achieve this, the content of said additives is between 5 and 20% by weight, typically above 10% by weight. must not.   The materials of group b) are not alloyed with a copper matrix and therefore have a thermal conductivity No significant effect on However, this material is relatively inexpensive. Of course It has been found that a content of 5 to 10% by weight is sufficient.   The additives of group c) cause the separation of the intermetallic components and thus additionally solidify Al in doped copperTwoOThreeOverlapping hardness effects due to particle hardening . Aluminum oxide particles are effective for copper matrix at high temperatures (> 500 ° C) However, the separation step takes place in the middle temperature range (200-500 ° C.). ), Which results in effective hardening, in which case the typical operation in which the valve seat ring is exposed Temperature matters. Than High hot hardness generally results in higher wear resistance.   The wear resistance of the valve seat ring is increased by using a solid lubricant such as graphite, MoSTwo, MnS, h -BN, CaFTwoAnd the addition of metal additives such as Mo, Co, W, etc. Can also produce oxide films with a lubricating effect at operating temperatures. Form.   The starting powder is one or more of the following substances:     5 to 20% by weight of Zn, any one of the elements Al, Be, Si, Mg, and Sn. 1-5% by weight The oxidation resistance, ie the corrosion resistance, is considerably increased during operation. Zn is an advantageous alloying component for the lowest possible reduction in thermal conductivity. this With respect to the above, addition of 5 to 30% by weight is not a problem.   The starting powder contains one or more of the following pulverulent substances having a non-uniform particle shape: Advantageously:     High raw strength Cu, electrolytic Cu, oxide reduced Cu, Mo, etc. 5 to 25% by weight.   Since the solidified copper used has circular particles and smooth particles, The resulting green compact has only a slight strength. The green strength is It can be increased considerably by adding a minute. "High raw strength Cu" A powder that has long, thin particles that look like fibers, which when crushed become entangled with each other, This results in a high strength of the formed form. Heat conduction The percentage is not affected by the addition of pure Cu and can be added at 5 to 25% by weight. The preferred range is 10 to 15% by weight.   The workability, especially machinability, of the dispersed solidified copper can be improved by adding one or more of the following substances. And is improved by:     a) chemical elements such as C (graphite), Te, Se 0.2-2% by weight;     b) sulfides such as MoSTwo, MnS, etc. 0.5 to 5% by weight;     c) oxides, such as MoOThree, WOThree, CoThreeOFour0.5 to 5% by weight;     d) compounds such as hexagonal BN, CaFTwo0.5-5% by weight.   The radial breaking strength of the valve seat ring, which should be given especially in the case of compression at the valve head, It is enhanced by the addition of one or more of the following substances:     a) 5 to 20% by weight of Zn, 0.1 to 5% by weight of Al or Sn, and the like;     b) M35 or T15 type tool steel, Ni-Cr-Si-Fe-B-Cu -Mo 5-30% by weight.   By means of a corresponding combination of the above-mentioned alloying additives, the starting powder mixture is in each case mounted on a valve seat ring. Can be adjusted optimally with respect to the characteristics required for   In the powder mixture according to the invention all described above, the valve seat ring The main advantage with regard to the production of is that the thermal conductivity is particularly high, ie at least 100 W / m · k. There is to be.   Example   Example 1   AlTwoOThreeCu solidified by internal oxidation with a content of 0.5% by weight -AlTwoOThreeMixing the powder with 0.3% by weight of a conventional compression simplifier and 800M N / mmTwoAt a compression pressure of 36.6 × 30.1 × 9 mm. . 8.4 g / cmThreeThe green compact having a compacted density of At 40 ° C., NTwoSintering was performed under a protective gas atmosphere consisting of 80% and 20% hydrogen. Burning The sintering density is 8.4 g / cmThreeMet. The sintered ring is subsequently pressed at 1600 MN / mmTwoAfter compression at a pressure of 8.8 g / cmThreeI made it.   Table 1 shows the measured density and hardness, and Table 2 shows the results obtained by the laser-flash method. 2 shows the measured values of the thermal conductivity.   Example 2   Al due to internal oxidationTwoOThreeDispersion solidified C produced with a content of 0.5% by weight u-AlTwoOThree90% by weight of powder, 10% by weight of water-evaporated powdery intermetallic hard phase And 0.3% by weight of a conventional compression simplifier. The intermetallic hard phase is cobalt 6 0% by weight, 30% by weight of molybdenum, 10% by weight of chromium and 3% by weight of silicon. Was. The powder mixture is compressed at 800 MN / mmTwoWith dimensions 36.6 × 30.1 × It was compressed into a 9 mm valve seat ring. The formed form has a compressed density of 8.2 g / cmThreeIt had. Pull The ring is then heated for 45 minutes at a temperature of 1040 ° C.Two80% and HTwo20% insurance Sintering in a protective gas atmosphere; sintering density 8.2 g / cmThreeMet. 8.7g / CmThreePost-compression to a density of 1600 MN / mmTwoPressure.   Table 3 shows the values of density and hardness, and Table 4 shows the values measured by the laser-flash method. The value of the thermal conductivity is shown.   The valve seat rings produced according to Examples 1 and 2 were designed for copper injection. Unexpected improvement in thermal conductivity over commercially available iron-based valve seat rings Indicated. This is clear from FIG. Curve 1 is the heat conduction of the valve seat ring according to Example 1. %, Curve 2 for the ring according to Example 2, curve 3 for Fe with copper implantation. The curve 4 shows the value of the valve seat ring commercially available from the present applicant. You.   The ring produced according to Example 1 has a hardness that allows its use in the inlet area of the internal combustion engine. On the other hand, the valve seat ring according to Example 2 can be used in the outlet area and In this case, it has excellent running characteristics. This proved experimentally, but the conditions The results are summarized in Table 5. The results of the engine experiments are summarized in Table 6 and shown in Fig. 2. did. The depression depth is the sum of the wear of the valve and the valve seat annulus. Inventive valve seat according to example 2 The rings were compared to Applicants' mass-produced material Como 12, which is used on a large scale.  The recess depth of the valve seat annulus of the present invention can be increased by increasing the thermal conductivity of the material, and the It was found to be lower than the sink ring's sinking depth.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 エッケハルト ケーラー ドイツ連邦共和国 ヴェター ウンターム ラートハウス 12 (72)発明者 キリット ダラル ドイツ連邦共和国 ラーデフォルムヴァル ト ローエングリン シュトラーセ ２ (72)発明者 エニール ヴイ ナドカルニ アメリカ合衆国 ノースカロライナ チャ ペル ヒル セットフォード コート 105────────────────────────────────────────────────── ─── Continuation of front page    (72) Eckehard Koehler             Germany Vetter Unterm               Rat House 12 (72) Inventor Kirit Dalal             Germany Radeformval             Troenglin Strasse 2 (72) Inventor Enil Vu Nadcarni             United States North Carolina Cha             Pell Hill Setford Court             105

Claims (1)

【特許請求の範囲】 １．高い耐摩耗性および耐蝕性ならびに高い熱伝導率を有する成形部材を粉末 冶金的に製造するための、特に内燃機関のための弁座環または弁案内部材を、少 なくとも約５０重量％の銅含量を有する出発粉末混合物の圧縮、焼結および場合 により後圧縮により製造するための材料において、出発粉末混合物が５０〜９０ 重量％の量のＣｕ含量含有基礎粉末および１０〜５０重量％の量のモリブデン含 有粉末状合金添加剤からなり、かつ基礎粉末が分散固化された銅粉末であること を特徴とする、高い耐摩耗性および耐蝕性ならびに高い熱伝導率を有する成形部 材を粉末冶金的に製造するための材料。 ２．分散固化された銅粉末がＡｌ2Ｏ3で固化されており、０．１〜１．１重量 ％のＡｌ2Ｏ3および０．５重量％未満の不純物を含有し、かつＣｕ−Ａｌ−溶融 物の噴霧および引き続きアルミニウムの選択的酸化のための酸化雰囲気下での加 熱により製造されたものである、請求項１記載の材料。 ３．合金添加剤が粉末状の、有利には水噴霧された金属間硬質相からなる、請 求項１または２記載の材料。 ４．金属間硬質相が以下の組成： モリブデン ２８〜３２重量％、有利には３０重量％ 、 クロム ９〜１１重量％、有利には１０重量％、 ケイ素 ２．５〜３．５重量％、有利には３重量％、 残分 コバルト、 を有する、請求項１から３までのいずれか１項記載の材料。 ５．粉末混合物中の金属間硬質相が約１０重量％の量で、および基礎粉末が約 ９０重量％の量で存在する、請求項４記載の材料。 ６．金属間硬質相が以下の組成： モリブデン ２８〜３２重量％、有利には３０重量％、 クロム ９〜１１重量％、有利には１０重量％、 ケイ素 ２．５〜３．５重量％、有利には３重量％、 残分 鉄、 を有する、請求項１から３までのいずれか１項記載の材料。 ７．粉末混合物中の金属間層が約１０重量％の量で、および基礎粉末が約９０ 重量％の量で存在する、請求項６記載の材料。 ８．硬質相からなる合金添加剤が以下の組成： タングステン 約６重量％、 モリブデン 約５重量％、 バナジウム 約２重量％、 クロム 約４重量％、 残分 鉄、 を有する高速度鋼（ＡｌＳｉ−型 Ｍ２；ＤＩＮ Ｓ−６−５−２）からなる、 請求項１または２記載の材料。 ９．粉末混合物中の硬質相が３０重量％までの量で、および基礎粉末が約７０ 重量％以上の量で存在する、請求項８記載の材料。 １０．硬質相からなる合金添加剤が以下の組成： モリブデン 約１１重量％ リン 約０．６重量％ 炭素 約１．２重量％ 残分 鉄、 を有するＭｏ−Ｐ−Ｃ−粉末からなる、請求項１または２記載の材料。 １１．粉末混合物中の硬質相および基礎粉末がそれぞれ約５０重量％の量で存 在する、請求項１０記載の材料。 １２．出発粉末混合物の以下の組成： 基礎粉末 約８０重量％、 モリブデン粉末 約１０重量％、 銅粉末 約１０重量％ を特徴とする、請求項１記載の材料。 １３．出発粉末混合物の以下の組成： 基礎粉末 約７９重量％、 モリブデン粉末 約１０重量％、 銅粉末 約１０重量％、および 酸化モリブデン 約１重量％ を特徴とする、請求項１記載の材料。 １４．基礎粉末が、付加的に硫化モリブデン（ＭｏＳ2）および／または硫化 第一マンガン（ＭｎＳ）および／または二硫化タングステン（ＷＳ2）および／ またはフッ化カルシウム（ＣａＦ2）および／またはテルル（Ｔｅ）および／ま たは炭酸カルシウム（ＣａＣＯ3）を、基礎粉末の量に対して、全体量で少なく とも１重量％から最高で３重量％含有する、請求項１から１３までのいずれか１ 項記載の材料 １５．高い耐摩耗性および耐蝕性および高い熱伝導率を有する成形品を粉末冶 金的に製造するための、特に内燃機関のための弁座環または弁案内部材を製造す るための方法において、請求項１から１４までのいずれか１項記載の出発粉末混 合物に、約０．３重量％の圧縮を簡易化する薬剤、例えばワックスを混合し、該 混合物を変形し、かつ密度約８．０ｇ／ｃｍ3を有する成形品に圧縮し、かつ引 続き保護ガス下で焼結させることを特徴とする、高い耐摩耗性および耐蝕性およ び高い熱伝導率を有する成形品を粉末冶金的に製造するための方法。 １６．約８０重量％の窒素および約２０重量％の水素からなる保護ガス下で、 温度約１０４０℃で約４５分間焼結を行う、請求項１５記載の方法。 １７．焼結した成形体を密度約８．８ｇ／ｃｍ3へ後圧縮させる、請求項１５ または１６記載の方法。 １８．Ａｌ2Ｏ3を用いて分散固化し、０．３〜１．１重量％の間にあるＡｌ2 Ｏ3含有量を有し、Ｃｕ−Ａｌ−溶融物の噴霧および引き続き酸化雰囲気下での 加熱により製造したＣｕ−Ａｌ2Ｏ3−粉末の、高い熱伝導率を有する耐摩耗性お よび耐蝕性成形品を粉末冶金により製造するための、特に弁座環または弁案内部 材を製造するための使用。 １９．出発粉末混合物が、以下に記載する物質または物質混合物： ａ）工具鋼Ｍ３５型またはＴ１５型、Ｎｉ−Ｃｒ−Ｓｉ−Ｆｅ−Ｂ−Ｃｕ−Ｍｏ ５〜３０重量％； ｂ）Ｗ、Ｍｏ、Ｎｂ、ＷＣ、ＴｉＣ、Ｂ4Ｃ、ＴｉＮ、ｃ−ＢＮ、ＴｉＢ2 ５〜 １０重量％； ｃ）Ｔｉ、Ｃｒ、Ｚｒ、Ｃｒ＋Ｚｒ、Ｂｅ、Ｎｉ＋Ｐ ０．５〜５重量％ を１種以上含有する、請求項１記載の材料。 ２０．出発粉末混合物が以下に記載する物質： Ｃｏ、Ｗ ５〜１０重量％ を１種以上含有する、請求項１記載の材料。 ２１．出発粉末混合物が以下に記載する物質： Ｚｎ ５〜２０重量％、元素Ａｌ、Ｂｅ、Ｓｉ、Ｍｇ、Ｓｎの１つ ０．１〜５ 重量％ を１種以上含有する、請求項１記載の材料。 ２２．出発粉末混合物が以下に記載する、不規則な粒子形を有する粉末状物質 ： 生強度の高いＣｕ、電解質−Ｃｕ、酸化還元されたＣｕ、Ｍｏ ５〜２５重量％ を１種以上含有する、請求項１記載の材料。 ２３．出発粉末混合物が以下の項目ａ）〜項目ｄ）に記載する物質： ａ）化学元素、例えばＣ（グラファイト）、Ｔｅ、Ｓｅ ０．２〜２重量％； ｂ）硫化物、例えばＭｏＳ2、ＭｎＳなど ０．５〜５重量％； ｃ）酸化物、例えばＭｏＯ3、ＷＯ3、Ｃｏ3Ｏ4など０．５〜５重量％； ｄ）六方晶ＢＮ、ＣａＦ2のような化合物 ０．５〜５重量％、 を１種以上含有する、請求項１記載の材料。 ２４．出発粉末混合物が以下に記載する物質： ａ）Ｚｎ、０．１〜５重量％のＡｌまたはＳｎなど５〜２０重量％； ｂ）工具鋼Ｍ３５型またはＴ１５型、Ｎｉ−Ｃｒ−Ｓｉ−Ｆｅ−Ｂ−Ｃｕ−Ｍｏ ５〜３０重量％ を１種以上含有する、請求項１記載の材料。 ２５．出発粉末混合物が請求項１８から２３までのいずれか１項記載の物質ま たは物質混合物の組み合わせを含有する、請求項１および請求項１８から２３ま でのいずれか１項記載の材料。 ２６．熱伝導率が少なくとも１００Ｗ／ｍ・ｋである弁座環または弁案内部材 を製造するための、請求項１および請求項１９から２４までのいずれか１項記載 の材料の使用。[Claims]   1. Powder molded parts with high wear and corrosion resistance and high thermal conductivity Valve seats or valve guides for metallurgical production, especially for internal combustion engines Pressing, sintering and, if appropriate, starting powder mixtures having a copper content of at least about 50% by weight The starting powder mixture is 50 to 90 A base powder containing a Cu content in an amount of 10% by weight and a molybdenum containing an amount of 10-50% by weight. Copper powder consisting of powdered alloy additive and base powder dispersed and solidified Molded part with high wear and corrosion resistance and high thermal conductivity characterized by Materials used to produce materials by powder metallurgy.   2. The dispersed and solidified copper powder is AlTwoOThree0.1 to 1.1 weight % AlTwoOThreeAnd less than 0.5% by weight impurities and Cu-Al-melt Spraying and subsequent application in an oxidizing atmosphere for selective oxidation of aluminum The material of claim 1, wherein the material is manufactured by heat.   3. The alloy additive comprises a powdered, preferably water-sprayed, intermetallic hard phase. 3. The material according to claim 1 or 2.   4. The intermetallic hard phase has the following composition: Molybdenum 28-32% by weight, advantageously 30% by weight , Chromium 9-11% by weight, advantageously 10% by weight, Silicon 2.5-3.5% by weight, advantageously 3% by weight, Residue cobalt, The material according to any one of claims 1 to 3, having:   5. The intermetallic hard phase in the powder mixture is in an amount of about 10% by weight and the base powder is 5. The material of claim 4, wherein the material is present in an amount of 90% by weight.   6. The intermetallic hard phase has the following composition: Molybdenum 28-32% by weight, advantageously 30% by weight, Chromium 9-11% by weight, advantageously 10% by weight, Silicon 2.5-3.5% by weight, advantageously 3% by weight, Residue iron, The material according to any one of claims 1 to 3, having:   7. The intermetallic layer in the powder mixture is in an amount of about 10% by weight and the base powder is about 90% by weight. 7. The material of claim 6, wherein the material is present in an amount by weight.   8. The hard phase alloy additive has the following composition: About 6% by weight of tungsten, About 5% by weight molybdenum, About 2% by weight of vanadium, About 4% by weight of chromium, Residue iron, High speed steel (AlSi-type M2; DIN S-6-5-2) having The material according to claim 1.   9. The hard phase in the powder mixture is in an amount of up to 30% by weight and 9. The material of claim 8, wherein the material is present in an amount equal to or greater than weight percent.   10. The hard phase alloy additive has the following composition: Molybdenum about 11% by weight About 0.6% by weight of phosphorus About 1.2% by weight of carbon Residue iron, The material according to claim 1, comprising a Mo—PC— powder having the following formula:   11. The hard phase and the base powder in the powder mixture are each present in an amount of about 50% by weight. 11. The material of claim 10, wherein the material is present.   12. The following composition of the starting powder mixture: About 80% by weight of base powder, Molybdenum powder about 10% by weight, Copper powder about 10% by weight The material according to claim 1, characterized in that:   13. The following composition of the starting powder mixture: About 79% by weight of base powder, Molybdenum powder about 10% by weight, About 10% by weight of copper powder, and Molybdenum oxide about 1% by weight The material according to claim 1, characterized in that:   14． The base powder additionally contains molybdenum sulfide (MoSTwo) And / or sulfide Manganese (MnS) and / or tungsten disulfide (WS)Two)and/ Or calcium fluoride (CaFTwo) And / or tellurium (Te) and / or Or calcium carbonate (CaCOThree), The total amount is less than the amount of the base powder 14. Any one of claims 1 to 13 wherein both contain from 1% by weight up to 3% by weight. Materials described in section   15. Powder molded parts with high wear and corrosion resistance and high thermal conductivity Manufacturing valve seat rings or valve guides for metal manufacturing, in particular for internal combustion engines 15. A method according to claim 1, wherein the starting powder is mixed. The compound is mixed with about 0.3% by weight of an agent which simplifies compression, for example, wax. Deform the mixture and have a density of about 8.0 g / cmThreeCompressed into a molded article with High wear and corrosion resistance and sintering characterized by continuous sintering under protective gas For producing molded articles having high thermal conductivity by powder metallurgy.   16. Under a protective gas consisting of about 80% by weight of nitrogen and about 20% by weight of hydrogen, The method of claim 15, wherein sintering is performed at a temperature of about 1040C for about 45 minutes.   17． The density of the sintered compact is about 8.8 g / cmThree16. The post-compression to Or the method of 16.   18. AlTwoOThreeAnd solidify using AlTwo OThreeContent, spraying of Cu-Al-melt and subsequently under oxidizing atmosphere Cu-Al manufactured by heatingTwoOThree-Abrasion resistance and high thermal conductivity of the powder; And valve seats for powder and metallurgical production of corrosion-resistant and molded articles Use for producing lumber.   19. The starting powder mixture is a substance or substance mixture described below: a) Tool steel M35 type or T15 type, Ni-Cr-Si-Fe-B-Cu-Mo   5-30% by weight; b) W, Mo, Nb, WC, TiC, BFourC, TiN, c-BN, TiBTwo  5- 10% by weight; c) Ti, Cr, Zr, Cr + Zr, Be, Ni + P 0.5-5% by weight The material according to claim 1, wherein the material contains one or more types.   20. The starting powder mixture has the following substances: Co, W 5-10% by weight The material according to claim 1, wherein the material contains one or more types.   21. The starting powder mixture has the following substances: Zn 5 to 20% by weight, one of the elements Al, Be, Si, Mg, Sn 0.1 to 5 weight% The material according to claim 1, wherein the material contains one or more types.   22. A powdery substance having an irregular particle shape, as described below, for the starting powder mixture : High raw strength Cu, electrolyte-Cu, redox Cu, Mo 5 to 25% by weight The material according to claim 1, wherein the material contains one or more types.   23. The starting powder mixture is a substance according to the following items a) to d): a) chemical elements such as C (graphite), Te, Se 0.2-2% by weight; b) sulfides, for example MoSTwo, MnS, etc. 0.5 to 5% by weight; c) oxides, such as MoOThree, WOThree, CoThreeOFour0.5 to 5% by weight; d) Hexagonal BN, CaFTwo0.5-5% by weight of a compound such as The material according to claim 1, wherein the material contains one or more types.   24. The starting powder mixture has the following substances: a) 5-20 wt% such as Zn, 0.1-5 wt% Al or Sn; b) Tool steel type M35 or T15, Ni-Cr-Si-Fe-B-Cu-Mo   5-30% by weight The material according to claim 1, wherein the material contains one or more types.   25. 24. The starting powder mixture as claimed in claim 18, wherein Or a combination of substance mixtures. The material according to any one of the preceding claims.   26. Valve seat ring or valve guide member with thermal conductivity of at least 100 W / mk 25. A method according to claim 1 for manufacturing a slab. Use of materials.
JP51611097A 1996-02-21 1997-02-21 Material for powder metallurgical manufacture of valve seat rings or valve guide members with high wear resistance Expired - Fee Related JP4272706B2 (en)

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DE19606270A DE19606270A1 (en) 1996-02-21 1996-02-21 Material for powder metallurgical production of molded parts, especially valve seat rings with high thermal conductivity and high wear and corrosion resistance
DE19606270.5 1996-02-21
PCT/EP1997/000837 WO1997030808A1 (en) 1996-02-21 1997-02-21 Material for the powder-metallurgical production of shaped parts, in particular valve seat rings or valve guides with high resistance to wear

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US6039785A (en) 2000-03-21

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